Pyrrolyl, hydroxo, and carbonate organometallic derivatives of nickel(II

May 1, 1989 - Deguang Huang , Olga V. Makhlynets , Lay Ling Tan , Sonny C. Lee , Elena V. Rybak-Akimova , and R. H. Holm. Inorganic Chemistry 2011 50 ...
0 downloads 0 Views 834KB Size
Download PDF
1895

Inorg. Chem. 1989, 28, 1895-1900 the clusters where X = N C O , C1, and Br, the lowest temperature exchange process averages all of the equatorial sites. Involvement of the axial carbonyls in this process occurs via a series of trigonal-twist steps and/or pairwise bridge-terminal CO-exchange steps. With [OsJ(CO),,]-, all of the carbonyls undergo exchange a t the same temperature, possibly through a rate-limiting trigonal twist of the O S I ( C O ) group. ~ Acknowledgment. This research was supported by a grant from the National Science Foundation (NSF-8714326).

Registry No. PPN[Os3CI(CO)Il],119909-83-0;PPN[Os3Br(CO),,], 119909-85-2;PPN[OS~I(CO)I,],119909-87-4; O~j(C0)12,15696-40-9; Me3N0, 1184-78-7; PPN[Os3(NCO)(CO)ll],119945-41-4; PPN(N3), 3801 1-36-8; CO, 630-08-0.

SupplementaryMaterial Available: Listings of positional and thermal parameters for H atoms, temperature factors, complete bond distances and angles, and crystallographicdata (26 pages); tables of calculated and observed structure factors (71 pages). Ordering information is given on any current masthead page.

Contribution from the Departamento de Quknica InorgBnica-Instituto de Ciencia de Materiales, Universidad de Sevilla-CSIC, 4107 1 Sevilla, Spain

Pyrrolyl, Hydroxo, and Carbonate Organometallic Derivatives of Nickel(I1). Crystal and Molecular Structure of [Ni(CH2C6H4-o-Me) (PMe3)(p-OH)I2-2,5-HNC4H2Me2 Ernesto Carmona,* Jose M. Marin, Pilar Palma, Margarita Paneque, and Manuel L. Poveda Received O c t o b e r 12, 1988

Pyrrolyl-organometallic derivatives of Ni(II), of composition Ni(R)(NC4H2X2)(PMe3)2 (X = H (la-5a), 2,5-Me (lb-5b); R = Me (l), CH2SiMe3(2), CH2CMe3(3), CH2CMe2Ph(4), 2,4,6-C6H2Me3(5)), have been obtained by treatment of the complexes t r a n ~ - N i ( R ) C l ( P M ewith ~ ) ~ the sodium salt of the pyrrolyl ligand. The action of wet C 0 2 upon solutions of 2a,b provides the (lo), possibly through the intermediacy of a dimeric hydroxide, [Ni(CH2SiMe3)carbonate Ni2(CH2SiMe3)2(C03)(PMe3)3 (PMe,)(p-OH)], (6). Hydroxides related to 6, [Ni(R)(PMe3)(pL-OH)l2 (R = CH2CMe2Ph(7),C H ~ C ~ (ti)), H S have been produced by reacting the corresponding monoalkyl chlorides with powdered NaOH and have been shown to react with C 0 2 with formation of carbonates analogous to 10, Ni2R2(C03)(PMe&(R = CH3 ( 9 ) , CH2SiMe3(lo), CH2C6H5(ll),C6H5(12)). The hydroxides readily form solid-state adducts, when crystallized in the presence of pyrrole or 2,5-dimethylpyrrole. NMR studies show these adducts are completely dissociated in solution, but an 0-H-N hydrogen-bonding interaction exists in the solid state, as revealed by the results of an X-ray structural determination, carried out with the o-methylbenzyl complex [Ni(CH2C6H4-o-Me)(PMep)(p-OH)],.2,5-HNC4H2Me2. The crystals are monoclinic, space group C2/c, with cell dimensions a = 15.598 (6) A, b = 12.655 (7) A, c = 17.705 (6) A, B = 111.72 (4)O, V = 3243.7 AS,and 2 = 4. The structure consists of dinuclear Ni2(v1CH2C6H4-o-Me)2(PMe3)2(p-OH)2 molecules and of 2,5-dimethylpyrrole molecules of crystallization, all of them showing crystallographic 2-fold symmetry. The Ni dimers have dihedral geometry, with the Ni atoms situated in a distorted square-planar environment.

Introduction Numerous studies have been reported concerning the carbonylation of nickel-carbon bonds.',2 Less well studied, although of increasing interest, is the analogous carboxylation r e a ~ t i o n . ~ Recent work by Yamamoto a n d co-workers has shown that t h e possibility of reductive elimination a t the metal center in complexes N i ( R ) X L 2 ( R = alkyl or aryl group), following carbonylation depends, among other factors, upon the strength of the Ni-X bond.4 T h e same arguments apply probably to the insertion of carbon dioxide but this process is less well documented. O n the other hand, the reactions of carbon dioxide with transition-metal compounds are very often complicated by the unpredictable effect of small amounts of water t h a t accompany C 0 2 a n d that a r e difficult to remove completely. This is in fact a pervasive feature of carbon dioxide chemistry and leads frequently to the formation of hydroxo or carbonate complexes.5 As part of continuing studies on the organometallic chemistry of nickel, we have carried out the preparation of some alkyl and aryl complexes, NiR(NC4H2X2)(PMe3)2,containing the pyrrolyl group. T h e study of their reactions with CO and C 0 2 a r e the subject of this paper. As discussed below, insertion of carbon monoxide is generally observed, but for carbon dioxide, formation Jolly, P. W.; Wilke, G. The Organic Chemistry of Nickel; Academic Press: New York, 1974. Jolly, P. W. Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Oxford, England, 1982; Vols. 6 and 8. (a) Braunstein, P.; Matt, D.; Nobel, D. Chem. Rev. 1988.88, 747. (b) Behr, A. Angew. Chem., Int. Ed. Engl. 1988, 27, 661. Yamamoto, T.; Kohara, T.; Yamamoto, A. Bull. Chem. SOC.Jpn. 1981, 54, 2161. Ibers, J. A. Chem. SOC.Rev. 1982, I I , 57.

0020-1669/89/1328-1895$01.50/0

of the binuclear carbonates, Ni2R2(PMe3)3(p-C03),takes place. The latter reaction does not have general application, but a general route to carbonates of this type, through the intermediacy of hydroxo-bridged species, [NiR(PMe3)(p-OH)I2, has been developed.

Results and Discussion ql-N-Pyrrolyl Complexes, Ni(R)(NC4H2Xz)(PMe3)2(1-5). Treatment of diethyl ether solutions of alkyl or aryl complexes of Ni(I1) of composition t r a n ~ - N i ( R ) C l ( P M e ~with ) ~ , the sodium salt of pyrrole or 2,5-dimethylpyrrole, NaNC4H2X2( X = H, Me), provides yellow crystalline derivatives, Ni(R)(NC4H2X2)(PMe3)2 (1-5) a s shown in eq 1. Spectroscopic studies clearly indicate

-

Ni(R)C1(PMe3)2+ N a N C 4 H 2 X 2 NiR(NC4H2X2)(PMe,), a, X = H ; b, X = M e 1,R=Me 2, R = C H 2 S i M e 3 3, R = C H 2 C M e 3 4, R = C H z C M e 2 P h 5, R = 2,4,6-C6HzMe3

+ NaCl

(1)

that compounds 1-5 exist in solution6 a s square-planar species, with trans phosphine groups and a monohapto, N-bonded pyrrolyl ligand. They can therefore be considered as alkane- (or arene-) amide complexes of n i ~ k e l . ~ - Rather '~ interestingly, l b forms (6) Solutions of compounds 1-5 are fairly stable to hydrolysis. This is at variance w i t h the behavior found for -Ni(CH2C6H4-o-Me)(NC,H2Me2)(PMe3)2,see: Carmona, E.; Marin, J. M.; Paneque, M.; Poveda, M. L. Organometallics 1987, 6, 1757. (7) Chisholm, M. H. Comprehensiue Coordination Chemistry; Wilkinson, G . , Gillard, R. D., McCleverty, J. A,, Eds.; Pergamon Press: Oxford, England, 1987; Vol. 2.

0 1989 American Chemical Society

1896 Inorganic Chemistry, Vol. 28, No. 10, 1989

C a r m o n a et al.

a solid-state adduct, NiMe(NC4H2Me2)(PMe3)2.HNC4H2Me2, this transformation but the well-known propensity of C O and other neutral ligands to induce reductive elimination in complexes of when crystallized in the presence of 2,5-dimethylpyrrole. N M R studies demonstrate this adduct is completely dissociated in C6D6 this type" should also be taken into account. Reactions of the Pyrrolyl Compounds NiR( NC4H2X2)(PMe3)2 solutions, but in the solid state there is a hydrogen-bonding interaction, N-H-N, between the N-H bond of the solvating pyrrole with CO, and H20. Hydroxo- and Carbonate-Bridged Complexes. As mentioned above, the pyrrolyl complexes 1-5 seem to be stable molecule and the N atom of the coordinated pyrrolyl ligand. This to the action of water. This markedly contrasts with the rapid proposal is substantiated by the shift to lower frequencies of hydrolysis undergone by the o-methylbenzyl derivative Niv(N-H) observed in the adduct, as compared with free 2,5-dimethylpyrrole (3350 and 3280 vs 3450 and 3340 cm-I, respec(CH2C6H4-o-Me)(NC4H2Me2)(PMe3)2,which affords6 the ditively) and also by the close similarity found with the related meric hydroxo-bridged species [Ni(CH2C6H4-o-Me)(PMe3)(padduct [Ni(CH2C6H4-o-Me)(PMe3)(p-0H)],-HNC4H2Me2, for OH)],. It is possible that an acid-base hydrolytic equilibrium which an X-ray analysis, to be discussed below, reveals a hy(eq 3) is set up for these pyrrolyl complexes, and that this drogen-bonding interaction between the O H ligands and the 2NiR(NC4H2X2)(PMe,), 2 H 2 0 * pyrrole N-H group." [NiR(PMe,)(p-OH)], 2 H N C 4 H 2 X 2+ 2PMe3 (3) Carbonylation of alkyl complexes of Ni(I1) of composition Ni(R)YL2, is known to provide isolable acyl species, N i ( C 0 R ) equilibrium lies well to the left for compounds 1-5, but far to the YL2, when Y is a halide, pseudohalide, or similar ligand.12 In right for the o-methylbenzyl complex. other cases, products resulting from reductive elimination (before To further investigate the chemical properties of the pyrrolyls or after insertion) or from other decomposition pathways may be 1-5, their reactivity toward C 0 2 has been studied. Compounds formed.', Recent work by Yamamoto and co-workers has shown 2a,b react with commercial CO, (3 atm, 20 "C) with production that if the Ni-COR and the Ni-Y bonds have similar strength, of the red crystalline species 10. Analytical, IR, and N M R data the weakening of both bonds, which is thought to precede reductive (see below) argue against formulation of 10 as a carboxylate elimination, can occur in a concerted manner, giving rise to the complex, Le., the product of the insertion of C 0 2 into the Ni-C products of the reductive elimination. Transition-metal-nitrogen bond of 2a,b, and suggest instead the existence of a carbonate bonds are generally weaker than corresponding M-0 bonds,I4 and ligand bridging two nickel centers, Ni2R2(PMe,),(p-CO3). If very for the group 8-10 metals, M - O and M - C bonds have comparable carefully dried C 0 2 is used for the reaction, formation of comthermodynamic ~ t a b i 1 i t y . l ~The reactions of 1-5 with C O are pound 10 is not observed. On the other hand, the reaction does therefore expected to provide the reductive-elimination products not have general applicability, and for example, compounds 3a,b following insertion, and to confirm this the carbonylation of some fail to yield the analogous carbonate complex under the same representative members of this series has been carried out, with conditions. Two mechanistic pathways can be envisaged to account the following results: (i) a solution of 2a in diethyl ether reacts for the formation of the carbonate. (i) The first is protolytic smoothly with C O (eq 2) with formation of Ni(CO),(PMe,), and cleavage of the Ni-N bond in compounds 1-5 by action of carco bonic acid, H 2 C 0 3 . This would produce initially a bicarbonate Ni(CH2SiMe3)(NC4H4)(PMe3), intermediate species, NiR(02COH)(PMe3)2,19 which by reaction Ni(CO)2(PMe,)2 M e 3 S i C H 2 C ( 0 ) N C 4 H 4 (2) with another molecule of the pyrrolyl complex would afford the observed carbonates. (ii) The second is direct action of C 0 2 (or the amide Me3SiCH2C(0)NC4H4,as the only detectable products. H2CO3) upon the equilibrium concentration of the hydroxo dimers, Therefore, the CO insertion is followed by reductive elimination. [NiR(PMe,)(p-OH)],, of eq 3. No clear distinction between these Complex 2b, which contains the more sterically demanding and alternatives can be achieved, but failure to generalize formation stronger electron-releasing -NC4H2Me2group, reacts with C O of the carbonate complexes by the reaction of CO, and water with as described above for 2a. (ii) The more sterically crowded mesityl complexes 1-5, Le., by route i, and the successful exploitation of derivative 5a reacts with C O in a way similar to that depicted route ii, that is, reaction of C 0 2 with [NiR(PMe,)(p-OH)], in eq 2, but more forcing conditions are required (3 atm of CO). complexes (see below), seem more in favor of the latter. Since Not unexpectedly, the even more sterically crowded complex 5b a general synthesis of the carbonates Ni2R2(PMe3),(p-C0,), does not react with C O (3 atm, 4 days, 20 "C). The well-known implicates the hydroxo species [NiR(PMe,)(p-OH)],, these will ortho effect may be invoked to account for these observations.'6 be discussed first. In concluding this section, it can be noted that while the alkyl(a) Hydroxo-Bridged Complexes [NiR(PMe,)(p-OH)]> Crystal (or aryl-) pyrrolyl complexes of Ni(I1) investigated in this work and Molecular Structure of the Solid-state Adduct [Niare thermally stable species, their acyl counterparts are not under (CH2C6H,-o-Me)(PMe3)(pOH)],-HNC4H2Me2. The first althe conditions studied and rearrange to the reductive-elimination kylnickel dimer containing bridging hydroxo ligands, [NiMeproducts. The decrease in the strength of the Ni-C bond in the (PMe,)(p-OH)],, was reported by Klein and KarschZ0in 1973. order Ni-C(a1kyl) > Ni-C(acyl)17 may have some influence in Related compounds have now been prepared by the same procedure, namely by treatment of the monoalkyls trans-Ni(R)XKlein, H. F.; Karsch, H. H. Chem. Ber. 1973, 106, 2438. (PMe,), with powdered N a O H in tetrahydrofuran or diethyl ether Yamamoto, T . ;Kohara, T.; Yamamoto, A. Bull. Chem. SOC.Jpn. 1981, solutions (eq 4). Compounds 6-8 have been obtained as yellow 54, 1720. Sacconi, L. Comprehensiue Coordination Chemistry; Wilkinson, G., 2Ni(R)CI(PMe3)2 2NaOH . Gillard, R. D., McCleverty, J. A,, Eds.; Pergamon Press: Oxford, [NiR(PMe,)(p-OH)], 2PMe, 2NaC1 (4) England, 1987; Vol. 5. Olovson, 1.; Jonsson, P.-G. In The Hydrogen Bond. Recent Deuelop6 , R = CH2SiMe, ments in Theory and Experiments; Schuster, P., Zundel, G., Sandorfy, 7, R = CH,CMe,Ph C., Eds.; North-Holland Publishing Company: Amsterdam, 1976; Vol. 8, R = CHZCGH, 11, Chapter 8, p 408. (a) Klein, H. F.; Karsch, H. H. Chem. Be?. 1976, 109, 2524. (b) crystalline solids that exhibit high solubility in common organic Carmona, E.; Gonzilez, F.; Poveda, M. L.; Atwood, J. L.; Rogers, R. solvents. The presence of a hydroxo ligand is manifested by the D. J . Chem. SOC.,Dalton Tram. 1980, 2108. (c) Komiya, S.; Akai, Y.; Tamaka, K.; Yamamoto, T.; Yamamoto, A. Organomerallics 1985, 4 , 1130. Yamamoto, T.; Sano, K.; Yamamoto, A. J . Am. Chem. SOC.1987, 109, (18) (a) Komiya, S.;Yamamoto, A,; Yamamoto, T. Chem. Lett. 1981, 193. 1092. (b) Tatsumi, K.; Nakamura, A,; Komiya, S.; Yamamoto, A.; YamaPurcell, K. F.; Kotz, J. C. Inorganic Chemistry; W. B. Saunders Commoto, T. J. Am. Chem. SOC.1984, 106, 8181. (c) McKinney, R. J.; Roe, D. C. J . Am. Chem. SOC.1986, 108, 5167. pany: Philadelphia, PA, 1977; p 854. Bryndza, H . E.; Calabrese, J. C.; Marsi, M.; Roc, D. C.; Tam, W.; (19) The reaction of PdMe2(PMe3)2with C 0 2 and H 2 0 affords the ?'-biBercaw, J . E. J . Am. Chem. SOC.1986, 108, 4805. See: Crutchley, carbonate compound rrans-PdMe(02COH)(PMe3)2. Chatt, J.; Shaw, B. L. J . Chem. SOC.1960, 1718. R. J.; Powell, J.; Faggiani, R.; Lock, C. J. L. Inorg. Chim. Acra 1977, Yamamoto, A. Orgonotransition Metal Chemistry; Wiley-Interscience: 2 4 , L15. New York, 1986; Chapter 6. (20) Klein, H. F.; Karsch, H. H. Chem. Eer. 1973, 1433.

+

+

-

+

+

-

+

+

Organometallic Derivatives of Ni(I1) Table I. 'H, 3'P, and 13C NMR Data (6;

cis-6 trans-6

cis-? trans-Ib

8c 9 10 1I d 12 c

'H ('JHP) 0.65 d (9.1)

J in Hz) for Complexes 6-12

PMe3 "CI'H} ('Jcp) 13.0 d (27.4)

0.60 d (8.8) 0.47 d (9.0)

13.2 d (29.1) 12.6 d (23.1)

d (8.7) d (7.2) d (8.4) br s br s br s

12.6 d (31.7) 12.1 d (27.1) 12.2 d (24.8) 12.7 br s 12.0 d (14.6) 12.0 br s

0.41 0.46 0.86 1.06 0.80 0.74

Inorganic Chemistry, Vol. 28, No. 10, 1989 1897

'3C11H)

IH 31P{'H} -8.2 s

-6.51 -2.80 -4.63 -6.59 -2.41 -4.56 -4.80

-9.5 s -7.5 s -8.5 -7.8 -10.7 -16.1 -12.3 -12.0

s s

br br br br

OH

CHI s

(3J~p)

CH3

-1.32 d (9.6)

0.52 s

-14.7 d (29.8)

0.5 s

-1.52 d (9.4) 0.24 d (8.9)

0.50 s 1.56 s

-14.5 d (32.1) 17.6 d (32.3)

3.5 s 33.1 s

0.15 d (8.8) 0.81 d (6.0)

1.56 s

16.8 d (34.5) 6.8 br s

33.7 s

s

s s

s s

s

s s s s

-1.06 br s 1.55 br s

0.76 s 0.53 br s

-16.2 br s 4.9 br s

-20.2 s 3.4 s

170.8 s 170.7 s 170.2 s 170.4 s

" 6 6.9-8.1 (m, CH,,,,), 40.1 (s, m e ) , 124.6, 126.5, and 127.6 (s, 1, 2, and 2 CH,,,,),153.9 (s, quat arom C). * 6 6.9-8.0 (m,CH,,,,),40.0 (s, m e ) , 124.6, 126.5, and 127.6 (s, 1, 2, and 2 CH,,,), 153.8 (s, quat arom C). c 6 6.8-7.5 (m, CH,,,,),121.5, 127.7, and 128.1 (s, 1, 2, and 2 CH,,,,),151.8 (s, quat arom C). d 6 7.1-7.9 (m, CH,,,,), 123.0, 128.0, and 129.1 (s, 1, 2, and 2 CH,,,,),148.9 (s, quat arom C). 6.7-7.0 (m, CH,,,,),121.8, 125.8, and 137.1 (s, 1, 2, and 2 CH,,,), 150.6 (s, quat arom C). observation of characteristic I R absorptions in the vicinity of 3600 cm-' and of high-field proton resonances (ca-2 to -6.5 ppm). The N M R data summarized in Table I unambiguously show that compounds 6 and 7 exist in solution as mixtures of the cis and trans isomers (structures I and II), while 8 is found exclusively R \Ni/

8\Ni/

H

R

'PMe3

Me3P/

I

/o\ Ni / \o/ Me3P R\

Ni

H

I1

as the trans isomer. For the methyl complex analogue, a mixture of cis and trans isomers had also been found in a ratio depending H19 on the polarity of the solvent.20 The cis and trans isomers of 6 and 7 readily interchange and are under thermodynamic equilibrium. In accord with this, the ' H N M R spectrum of an approximately equimolar solution of 7 and 8, shows, in addition to signals due to 7 and 8, new sets of reasonances that can be attributed to the cis and trans isomers of the mixed derivative (Me3P)(PhMe2CCH2)Ni(p2-OH)2Ni(CH2C6H5)(PMe3). It is likely that traces of PMe, present in solution induce dissociation C13 of the dimers to the 16-electron monomeric species N i R ( 0 H ) (PMe3)2. Formation of these intermediates and ulterior regenFigure 1. ORTEP diagram and atom-labeling scheme for [Nieration of the dimer would also imply exchange between coor(CH2C,H4-o-Me)(PMe3)(p-OH)]'*HNC4H2Me2. dinated and free PMe,, and this has been confirmed by N M R studies of solutions that contain the hydroxides 6-8 plus added Table 11. Crystal Data for PMe,. [Ni(CH2C6H4-o-Me)(PMe3)(pOH)12-HNC4H2Me2 There is increasing interest in the structural characteristics of empirical formula C28H47N02P2Ni2 hydroxo derivatives of transition metals.21 This, and the already color brown-red mentioned formation of solid-state adducts between hydroxo cryst size, mm 0.40 X 0.40 X 0.67 compounds of nickel(I1) and pyrrole derivatives have prompted space group c 2j c us to undertake a single-crystal X-ray study of one of these adcell dimens ducts. The already reported6 o-methylbenzyl complex [Ni15.598 (6) a, A (CH2C6H4-eMe)(PMe3)(p-OH)]2.HNC4H2Me2, has been chosen 12.655 (7) b, 8, 17.705 (6) for convenience. In addition to intrinsic interest, determination c, A 11 1.72 (4) 0,deg of the structure of this compound was of importance for comZ 4 parative purposes. W e have reported recently the results of an v,A3 3243.7 X-ray study carried out with the trimetallic compound Ni31.25 Dcald, g cm-3 (CH2C6H4-o-Me)4(PMe3)2(p-OH)2, and shown that the structure wavelength, A 0.710 69 can be described6 as consisting of a binuclear hydroxo-bridged temp, OC 19 fragment, [Ni(CH2C6H4-o-Me)(PMe3)(p-oH)]2 and a Nimol wt 609.0 ( C H 2 C 6 H 4 - ~ - M e group, )2 the latter being stabilized by coordilinear abs coeff, cm-l 12.78 nation of the nickel center to the two O H groups of the dimeric 28 range, deg 0-60 no. of unique data 6768 hydroxo unit. Compounds 6-8 and related derivatives provide no. of data with [ I 2 3u(1)] 2012 the dimeric hydroxo fragment of the Ni, species. Not surprisingly, 0.057 R(F) the donor properties of the bridging O H ligands are manifested 0.062 RdF) again, although this time by their engagement in a fairly strong (21) (a) Ardon, M.; Bino, A. Inorg. Chem. 1985, 24, 1343. (b) Comarmod, J.; Dietrich, B.; Lehn, J.-M.; Louis, R. J . Chem. SOC.,Chem. Commun.

1985, 74. (c) Thompson, L. K.; Mandal, S.K.; Gabe, E. J.; Lee, F. L.; Addison, A. W. Inorg. Chem. 1987,26,657. (d) Babcock, L. M.; Day, V. W.; Klemperer. J . Chem. SOC.,Chem. Commun. 1988, 519. ( e ) Rochon, F. D.; Morneau, A.; Melanson, R. Inorg. Chem. 1988, 27, 10.

hydrogen-bonding interaction with the N-H bond of 2,5-dimethylpyrrole. An ORTEP drawing is shown in Figure 1. The compound consists of a dinuclear nickel-containing dihedral molecule (the two dihedral planes intersecting at the 0(3)-0(3)' direction; dihedral angle = 133.6') and of a molecule of crystallization of 2,5-dimethylpyrrole, both of them situated on a 2-fold

1898 Inorganic Chemistry, Vol. 28, No. 10, 1989

Carmona e t al.

Table 111. Bond Distances (A) for [ Ni(CH2C6H,-o-Me) (PMe,) (+-OH)]2-HNC4H2Me2

Ni( I)-P(2) Ni(1)-O(3) Wi(1)-0(3)’ Ni( I)-C(4) P(2)-C(21) P(2)-C(22) P(2)-C(23) C(4)-C(5) C(5)-C(6) C(5)-C(IO) C(6)-C(61)

2.122 (2) 1.920 (4) 1.917 (4) 1.946 (7) 1.813 (9) 1.812 (9) 1.821 (8) 1.49 ( I ) 1.39 (1) 1.38 (1) 1.49 ( I )

C(7)-C(8) C(6)-C(7) C(8)-C(9) C(9)-C(10) N(ll)-C(12) N(ll)-C(12) N(ll)-C(13) N(ll)-C(13) C(12)-C(121) C(12)-C(13) C(13)-C(13)

1.39 (1) 1.40 (1) 1.35 ( I ) 1.38 ( I ) 1.33 (1) 1.33 ( I ) 2.14 (1) 2.14 (1) 1.48 (2) 1.37 (2) 1.31 (4)

Table IV. Bond Angles (deg) for

[Ni(CH2C6H4-o-Me)(PMe3)(+-OH)]2-HNC4H2Me2 0(3)-Ni(I)-P(2) O(3)-Ni( I)-P(2) 0(3)-Ni(l)-0(3)’ C(4)-Ni(l)-P(2) C(4)-Ni(l)-O(3)’ C(4)-Ni(1)-0(3) C(2l)-P(2)-Ni(l) C(22)-P(2)-Ni( 1) C(22)-P(2)-C(21) C(23)-P(2)-Ni( I ) C(23)-P( 2)-C(2 1) C(23)-P(2)-C(22) Ni( 1)-0(3)-Ni( I)’ C(5)-C(4)-Ni(l) C(6)-C(j)-C(4) C( lO)-C(j)-C(4) C(lO)-C(5)-C(6) C(61)-C(6)-C(5) C(7)-C(6)-C(5) C(7)-C(6)-C(61)

97.0 (2) 172.3 (2) 78.2 (3) 89.8 (2) 173.1 (3) 95.0 (3) 114.0 (3) 118.4 (3) 102.9 (5) 113.8 (3) 103.4 (4) 102.5 (4) 91.0 (2) 111.2 (5) 121.8 (8) 120.1 (8)

118.0 (9) 121.0 (9) 119.5 (9) 119.5 (9)

C(8)-C(7)-C(6) C(9)-C(8)-C(7) C(lO)-C(9)-C(8) C(9)-C(IO)-C(5) C(l2)-N(ll)-C(l2) C(l3)-N(ll)-C(l2) C(l3)-N(ll)-C(12) C( 13)-N( 11)-C(12) C(13)-N(I 1)-C(12) C( 13)-N( 1 I)-C( 13) C( 121 )-C( 12)-N( 1 1) C(l2l)-C(I2)-N(ll) C( l3)-C( 12)-N( 11) C(l3)-C(l2)-N(ll) C( l3)-C( 12)-C( 121) C( 12)-C( 13)-N( 11) C(l2)-C(l3)-N(ll) C( 13)-C( 13)-N( 1 1 ) C(I3)-‘2(13)-N(ll) C(13)-C(13)-C(12)

120.2 (10) 120.5 (10) 119.5 (10) 122.4 (9) 111.3 (6) 37.9 (9) 73.4 (10) 73.4 (10) 37.9 (9) 35.5 (9) 122.0 (12) 122.0 (12) 105.5 (15) 105.5 (15) 132.4 (15) 36.6 ( 8 ) 36.6 ( 8 ) 72.2 ( 5 ) 72.2 ( 5 ) 108.8 ( I O )

crystallographic axis that contains the pyrrolic N-H group. The geometry around each Ni atom is that of a distorted planar square, the O(3)-Ni( I)-O(3)’ bond angles being less than 90°, as expected from the fact that O(3) and O(3)’ are bridging atoms. Consequently, the 0-Ni-C angles are greater than 90°, while the P-Ni-C ones remain unchanged from the ideal square-planar geometry (see Table 1V). Each Ni atom is almost symmetrically bonded to the two hydroxyl groups, at Ni-0 separations of 1.920 (4) and 1.917 (4) 8, (for N i ( l ) - 0 ( 3 ) and Ni(1)-0(3)’, respectively). Not unexpectedly, these values are appreciably smaller than all the N i - 0 bond distances in Ni,(CH2C6H4-o-Me)4(PMe3)2(p3-0H)2.6 An interesting feature of the compound is the existence of a symmetrical bifurcated” H bridge between the pyrrolic N atom and the 0 atoms of the nickel dimer. The N - O separations within the bridge are 3.12 (1 ) A (1 .OO (1) 8, for the N-H bond, 2.230 (5) 8, for the 0 - H interactions) and the angles at the hydrogen ( N ( 1 l ) - H ( l9)-0(3) and N ( l I)-H(l9)-0(3)’) are both 147.1

(]I0. (b) Binuclear Carbonate Complexes (Me3P),RNi(~,-q1,q2CO,)NiR(PMe,). The reaction of the pyrrolyl compounds 2a,b,

with high-purity commercial carbon dioxide under pressure (2-3 atm). affords the red crystalline complex 10. Carefully dried CO, does not react with 2 under the same conditions, and in fact, deliberate addition of water to the reaction system is advisable, particularly for large-scale preparations. 10 is a binuclear species as revealed by a cryoscopic molecular weight determination. Its 1R spectrum displays a strong absorption a t ca. 1510 cm-l, suggesting the existence of a carbonate ligand. Further evidence for this comes from the observation of a characteristic 13C N M R resonance a t ca. 170 ppm. On the basis of this and other data, 10 can be formulated as a binuclear, carbonate-bridged complex (eq 5 ) . This has been confirmed by an X-ray study which shows CO, + H,O 2NiR(NC,H,X2)(PMe3), Ni,R2(CO3)(PMe3), + PMe, 2HNC4H2X2 ( 5 )

+

-+

that the bridging carbonate ligand is dihapto bonded t o one of the nickel atoms and monohapto bonded to the other. A drawing

Figure 2. Drawing of the molecule of 10.

of the molecule of 10 is shown in Figure 2. The structure is however of poor quality (see Experimental Section), and therefore, the results of this study will not be discussed. There is precedent in the literature*, for structures of the type found for 10, and in addition, we have shown recently that the metalacycle t

I

(Me3P),Ni(CH2cMe2-o-c6H4)reacts with C 0 2 and H 2 0 , to provide2, the neophyl analogue of 10. Extension of the above synthetic procedure to other carbonate derivatives has proved unsuccessful. An alternative (and on the other hand general) route to these carbonates has been developed by means of hydroxo compounds of the type described in the last section (eq 6). By this route,24 new compounds of composition H

R\N,/ Me3P

OLNi/ \ O /H

R(PMe3)

+

PMe3

+

CO,

\PMe3(R)

-

PMe3

+

R-NI-0-C

I

\o/

H 2 0 (6)

\R

PMe3

Ni2R2(C03)(PMe3), (R = CH, (9), CH2SiMe3 ( l o ) , C H ~ C ~ H S ( l l ) , C6H5(12)) can be readily obtained and characterized. The transformation of eq 6 has also proved a more convenient procedure for the synthesis of t h e neophyl derivative, Ni2(CH2CMe2Ph),(C03)(PMe3),,which, as indicated above, had been produced previously by a different route.23 Compounds 9-12 a r e yellow to red crystalline solids, readily soluble in common organic solvents. Their I R spectrum is dominated by a strong absorption a t ca. 1500 cm-l, due to the carbonate ligand. They exhibit fluxional behavior in solution, but while 10 and the neophyl analogue give two separate 31PresoNMR nances (ca. 2:l ratio) in the room-temperature 31P{1H) spectrum, the remaining compounds provide an average broad signal a t approximately -10 ppm. T h e fluxional process responsible for this behavior has been described in detail elseFormation of these carbonates by action of CO, on the hydroxo complexes is an acid-base reaction. Whether this acid-base process is adequately represented by reaction 6 or requires catalytic or stoichiometric quantities of water (eq 7 )

+ PMe, + H2CO3

[NiR(PMe3)(p-OH)I2

-

Ni2R2(CO3)(PMe3),+ 2 H 2 0 (7)

cannot be ascertained. It should be recalled that complete removal of small amounts of water from C 0 2is difficult to achieve. Finally, it should be mentioned that in order to avoid the unnecessary loss of PMe, implied in the isolation of the hydroxo compounds (22) Yoshida, T.; Thorn, D. L.; Okano, T.; Ibers, J. A,; Otsuka, S . J . Am. Chem. SOC.1979, 101, 4212. (23) (a) Carmona, E.; Palma, P.; Paneque, M.; Poveda, M. L.; GutibrrezPuebla, E.; Monge, A. J . Am. Chem. SOC.1986, 108, 6424. (b) Carmona, E.; Gutibrrez-Puebla, E.; Marin, J. M.; Monge, A,; Paneque, M.; Poveda, M . L.; Ruiz, C. J . Am. Chem. SOC.,in press. (24) A recent report by Caulton has described the formation of a rhodium carbonate complex from the reaction of C 0 2with a dimeric rhodium hydroxo species. See: Lundquist, E. G.; Folting, K.; Huffman, J. C.; Caulton, K. G. Inorg. Chem. 1987, 26, 205.

Organometallic Derivatives

Inorganic Chemistry, Vol. 28, No. 10, 1989 1899

of Ni(I1)

2,4,6-C6H2Me3(Sa,b). The results are described below. (a) Reaction of Compounds 2 with CO. C O was bubbled through a solution of compounds 2 (ca. 2 mmol) in Et,O (30 mL) at room temperature and atmospheric pressure, for I O min, during which time the color of the solution changed from red-orange to pale yellow. The solvent was evaporated under reduced pressure and the resulting pale yellow oily residue demonstrated by IR and 'H, "C, and 31P NMR spectroscopies to contain a mixture of the amide Me3SiCHzC(0)NC4H4and Ni(C0)2(PMe3)z(reaction of 2a). Me3SiCH2C(0)NC4H4:'H NMR (200 MHz, C6D.5) 6 4 . 1 0 ( S , 9 H, SiMe,), 2.10 ( s , 2 H, CH2Si),6.05 and 7.10 (s, 2 H and 2 H, NC4H4);I3C('H)NMR (C6D6) 6 -1.6 (SiMe3), 27.1 (SiCH2), 112.3 and 119.1 (NC,H,), 168.8 (CO); IR (Nujol mull) QO co at 1700 cm-I. For the 2,5-dimethylpyrrolyl complex, 2b, the spectroNi2R2(C03)(PMe3)3 scopic studies also indicate the formation of the corresponding amide, 0 Me3SiCH2C(0)NC4H2Mez,and the carbonyl Ni(C0)2(PMe3)z. O I 1 Me3SiCHzC(0)NC4HzMez:'H NMR (200 MHz, C6D6)6 -0.08 (s, 9 " N I ( O ) " + COZ + R-C-0-C-R (8) H, SiMe3),2.04 and 2.21 (s, 3 H and 3 H, NC4H2Me2),2.19 (s, CH2Si), 5.71 and 5.81 (s, 1 H and 1 H, NC4H2Me2);I3C('H}NMR (C&) 6 -1.7 the carbonates react in the expected manner, although for sim(SiMeJ, 12.9 and 16.0 (NC4H2Me2),32.1 (CH2Si), 105.9 and 110.7 plicity, only the reactions of 9 and 12 have been studied in detail (CH pyrrole), 125.0 and 129.0 (quaternary C, pyrrole), 173.3 (CO); IR (see Experimental Section). (Nujol mull) vC- at 1710 cm-I. (b) Reaction of Ni(2,4,6-C6H2Me3)(NC4H2X2)(PMe3)z (5) with CO. Experimental Section Complex Sa does not react with CO under ambient conditions. NeverMicroanalyses were by Pascher, Microanalytical Laboratory, Bonn. theless, when a solution of 5a was pressurized (2-3 atm CO) and stirred The spectroscopic instruments used were Perkin-Elmer Models 577 and for 4-5 h at room temperature, it was observed to become colorless. 684 for IR spectra and Varian Model XL-200 for NMR. ,'P shifts were Subsequent spectroscopic studies (IR, 'H, 13Cand I'P NMR) indicated measured with respect to external 85% H3P04. I3CNMR spectra were and the comthe formation of the amide 2,4,6-C6H2Me3C(0)NC4H4 referenced by using the "C resonance of the solvent as an internal plexes Ni(C0)2(PMe3)2and Ni(C0)3(PMe3). 2,4,6-C6HzMe3C(0)standard but are reported with respect to SiMe4. NC4H4: 'H NMR (200 MHz, C6D6) 8 1.95 (s, 6 H, 2 Me), 2.10 ( s , 3 All preparations and other operations were carried out under a proH, Me), 6.00, 6.20, 6.32, and 7.70 (br s, 1, 1, 1, and 1 H, NC4H4),6.62 tective blanket of oxygen-free nitrogen, following conventional Schlenk (s, 2 H, C6HzMe3);13C('H)NMR (C6D6) 6 18.6 (2 Me), 20.8 (Me), techniques. Solvents were dried and degassed before use. The petroleum 113.3, 113.6, 118.0, and 120.8 (CH pyrrole), 128.2 (CH, C6H2Me3 ether used had a boiling point range of 40-60 "C. NaNC4H4 and group), 132.2, 134.4, and 139.2 (quaternary aromatic carbons), 168.0 NaNC4H2-2,5-Me2were prepared by reacting NaH with pyrrole and (CO). IR (Nujol mull): uco at 1710 cm-I. The 2,5-dimethylpyrrolyl 2,5-dimethylpyrrole, respectively. The anhydrous C02,required for some derivative 5b did not react with CO when stirred for 4 days, under 2-3 of the preparations, was obtained by reaction of BaCO, with HzSO4 and atm of CO. purified by several trap-to-trap distillations. The alkyl derivatives Dimeric p-Hydroxide Derivatives of Composition [NiR(PMe,)(w t r ~ n s - N i ( R ) C l ( P M e ~(R) ~ = CH3,25 CH2SiMe3,'2b CH2CMe3,26 OH)I2. These p-hydroxide derivatives were obtained from the parent CH2CMe2Ph,'2bCHzC6HS,272,4,6-C6H2Me3") were prepared as decompounds Ni(R)C1(PMe3)2,following the method described below for scribed in the literature. The ligand PMe3 was obtained by the method the benzyl derivative [Ni(CHZC6H,)(PMe3)(p-OH)1, (8). of Wolfsberger and Schmidbaur.28 All new compounds gave satisfactory A mixture of Ni(CH2C6H5)C1(PMe3)2 (0.5 g, ca. 1.5 mmol) and an elemental analyses. excess of powdered NaOH (0.5 g) was stirred in T H F (30 mL) at room Pyrrolyl Derivatives of Composition Ni(R)(2,5-NC4H2X2)(PMe3)2 temperature for 3-4 h. The color of the solution changed from red-brown (la,b-Sa,b). All the pyrrolyl complexes reported in this work have been to orange. The solvent was stripped-off and the residue exthcted with prepared by reacting the corresponding alkyl derivative Ni(R)C1(PMe3)2 a mixture of petroleum ether-diethyl ether (1:2) and centrifuged. After with the appropriate pyrrolyl sodium salt NaNC4H2X2(X = H, Me), partial evaporation of the solvent, cooling of the resulting solution furfollowing the procedure described below for complex 3a, Ninished dark-red crystals of the title compound in nearly quantitative yield. (CH2CMe3)(NC4H4)(PMe3)2. Similar procedures allowed the isolation of the related derivatives To a stirred solution of the alkyl Ni(CH2CMe3)C1(PMe3)2(0.73 g, [Ni(CH2CMe2Ph)(PMe3)(p-OH)]2 (7)(as brown yellow needles, from ca. 2.3 mmol), in E t 2 0 (40 mL), cooled at -30 "C, an excess of NaN( 6 ) (red-brown petroleum ether), [Ni(CH2SiMe3)(PMe3)(p-0H)1, C4H4 (3 mL of a 1 M solution in THF) was added. The resulting plates, from petroleum ether) and [Ni(C6H,)(PMe3)(p-0H)l2(yellow mixture was stirred for 15 min, slowly warmed to room temperature, and microcrystals, from mixtures of petroleum ether-dichloromethane (2:1)). then further stirred for 4-5 h, during which time the color of the solution The latter complex was not analyzed, and it is reported only for comchanged from brown-red to yellow-orange. The solvent was removed parative purposes. Compound 6 can also be prepared, albeit in lower under vacuum and the residue extracted with Et20 (20 mL). After yields, by the following procedure. To a stirred solution of the dialkyl centrifugation and partial concentration of the solution, cooling at -30 Ni(CH2SiMe3)2(PMe3)2 (0.6 g, 1.5 mmol) in acetone (30 mL) was added "C for several hours provided orange crystals of the desired compound a drop of water. The stirring was continued for 10-12 h and the solvent (yield 60%). removed under vacuum. The residue was dissolved in petroleum ether, The complexes Ni(CH2SiMe3)(NC4H4)(PMe3)z (2a) and the neophyl and after centrifugation, concentration and cooling of the solution at -30 analogue (4a) were also isolated as yellow-orange crystals in 60% yield "C, red-brown plates of the dimeric p-hydroxo complex were obtained from E t 2 0 solutions. The more soluble Ni(Me)(NC4H4)(PMe3)2( l a ) in 40% yield. and Ni(2,4,6-C6H2Me3)(NC4H4)(PMe3)2 (Sa) were crystallized from Reaction of the Dimeric p-Hydroxo Derivatives with C02: Synthesis petroleum ether, in comparable or higher yields. The 2,5-dimethylof the Carbonate-Bridged Complexes (Me3P)(R)Ni(p2-v2,t$-C03)Nipyrrolyl derivatives l t 5 b were prepared similarly, but the dry residues (R)(PMe3)z. The suspension containing the appropriate dimeric p-hyof the reactions were extracted with a mixture petroleum ether-diethyl droxide complex, obtained by stirring the alkyl derivative with NaOH, ether and worked up by following the same procedure, to afford redwas filtered into a thick-wall vessel, which was pressurized with 3 atm orange crystalline materials in 60-70% yields. The methyl derivative of C 0 2 and stirred at room temperature for 3 h. The solvent was evapNi(Me)(NC4H2Me2)(PMe3)2(lb) was sometimes obtained mixed with orated under vacuo and the resulting residue extracted with the adequate a small amount of the pyrrole adduct Ni(Me)(NC4H2Me2)(PMe3)2. solvent (see below) and centrifuged. Partial evaporation and cooling at HNC4H2Me2. -30 OC provided crystals of the desired compounds in almost quantitative Reaction of the Pyrrolyl Derivatives with CO. The study of the reyields: R = Me (9), yellow-brown plates from petroleum ether-diethyl activity of these complexes with CO has been carried out with both the ether (1:2); R = CH2SiMe3(lo), dark-red needles from petroleum ether; pyrrolyl and the 2.5-dimethylpyrrolyl derivatives of CH2SiMe3(2a,b) and R = CHzC6HS( l l ) , orange needles, from diethyl ether; R = C6H5 (12), yellow microcrystals, from petroleum ether-diethyl ether (1:2). The CH2SiMe3derivative 10 was also obtained by the reaction of petroleum (25) Klein, H. F.; Karsch, H. H. Chem. Ber. 1972, 105, 2628. ether solutions of the pyrrolyl derivatives Ni(CH2SiMe3)(NC4H2X2)(26) Carmona, E.; Paneque, M.; Poveda, M. L.; Rogers, R. D.; Atwood, J. (PMe,), (ca. 1 mmol in 40 m L of solvent) with wet C02 (2.5 atm, 24 L. Polyhedron 1984, 3, 317. h) in 60% yield. (27) Carmona, E.; Paneque, M.; Poveda, M. L. Polyhedron 1989, 8, 285. Reaction of the Bridging Carbonate Derivatives 9 and 12 with CO. A (28) Wolfsberger, W.; Schmidbaur, H. Synrh. React. Inorg. Met.-Org. solution of the carbonate (ca. 1 mmol) in 0.5 mL of C6D6was stirred Chem. 1974, 4 , 149.

[Ni(R)(PMe3)(p-0H)l2,the carbonates 9-12 can be obtained by direct action of C 0 2 upon the supernatant which results after the separation of the excess of powdered N a O H in reaction 4. The carbonate-neophyl species N i 2 ( C H 2 C M e 2 P h ) 2 ( C 0 3 ) (PMe3)3has been shown to undergo an unusual transformation in t h e presence of carbon monoxide, which yields, in addition to Ni(CO)n(PMe3)4-n( n = 2, 3), carbon dioxide and the anhydride (RC0)20.The generality of this carbonate-carbonyl conproportionation reaction23 has been attested by studying the interaction of the carbonates 9-12 with CO. As shown in eq 8, all

-

II

Inorg. Chem. 1989, 28, 1900-1904

1900

under 2 atm of CO for 15-30 min. The color of the solution became pale yellow. IH, ,IP, and I3C NMR studies of the resulting solution, together with the IR spectrum of the residue obtained by removal of the solvent, allowed the identification of the organic anhydride (RC0)20 and of the carbonyls Ni(C0),(PMeJ2 and Ni(CO)3(PMe3) as the only detectable products. X-ray Structure Determination. The air-sensitive crystal of [Ni(CH2C6H,-o-Me)(PMe3)(p-OH)]2*HNC4H2Me2 was put in a glass capillary under nitrogen atmosphere and mounted on the goniometer head of an Enraf-Nonius CAD4 diffractometer. Data were collected by using w-28 scans and reduced, and a set of 2012 unique reflections was used in subsequent calculations. The analysis of the Patterson map permitted the location of the Ni atoms, the rest of the non-H atoms being located by means of successive cycles of Fourier synthesis. The H atoms were geometrically placed, except the one corresponding to the N H group (extracted from a Fourier difference map). The H atoms corresponding to the OH groups could not be found, and its consideration was omitted. An empirical absorption correction29was applied at the end of the isotropic refinement of the non-H atoms but some degree of disorder, nonresolvable from thermal motion, was encountered in the pyrrolyl carbon atoms. The anisotropic refinement converged at R = 0.057, using unit weights. A summary of crystal data is given in Table 11. All

computations were made with the Oxford CRYSTALS package.,O The atomic scattering factors were taken from ref 31. Figure 2 shows the geometry of the molecule of 10. Although the structure has been solved in the triclinic space group PI, all attempts to refine it below R N 20 (convergence of isotropic refinement) have proved unsuccessful, and thus no crystallographic data are included. Acknowledgment. Generous support of this work by the Agencia Nacional d e Evaluaci6n y Prospectiva is very gratefully acknowledged. P.P. and M.P. thank t h e Ministerio d e Educacidn y Ciencia for support of a research grant. Supplementary Material Available: Analytical data for complexes 1-11 and 'H, 31P,and I3C NMR data for the pyrrolyl complexes 1-5 (Tables A, B, and C), fractional atomic coordinates and thermal parameters for [Ni(CH2C6H4-o-Me)(PMe3)(p-OH)]2-HNC4H2Me2 (Tables D and E) (4 pages); observed and calculated structure factors (Table F) (19 pages). Ordering information is given on any current masthead page. (30) Watkin, D. J.; Carruthers, J. R.; Betteridge, P. W. 'CRYSTALS"; Chemical Crystallographic Laboratory: Oxford, England, 1985, Issue

9.

(29) Walker, N.; Stuart, D. Acta Crystallogr., Sect. A 1983, ,439, 158.

( 3 1) International Tables for X-ray Crystallography; Kynoch: Birmingham,

England, 1974; Vol. IV.

Contribution from the Departments of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, Quebec H3A 2K6, Canada, and Concordia University, 1455 de Maisonneuve Boulevard West, Montreal, Quebec H3G 1M8, Canada

Preparation of (q-C5H5)W(C0)2(PPh3)SRand Insertion of CS2 To Give the Thioxanthates (q-C5H5)W (C0)2S2CSR (R = CHMe2, CH,Ph, 4-C6H4Me). Crystal Structure of (q-C5H5)W(C0)2S2CSCH2Ph Alan Shaver,*Ja Bernadette So0 Lum,la Peter Bird,Ib and Kevin Arnoldlb Received September 29, 1988 Treatment of (&H5)W(C0),(PPh3)H with methyllithium and subsequently with RS(phth) gave (&,H,)W(CO),(PPh,)SR as a mixture of cis and trans isomers, where phth = phthalimido and R = CHMe,, CH2Ph,and 4-C6H4Me. These isomers react with CS2 to give the thioxanthate complexes (q-C,H5)W(C0),S2CSR wherein the CS2 has inserted into the W-SR bond. The structure of (i&H5)W(C0)2S2CSCH2Ph was determined: C2/c, a = 27.106 (20) A, b = 10.050 (5) A, c = 13.108 (13) A, p = 66.18 (7)O, V = 3266.4 A), and Z = 8. The cis isomer reacted more rapidly than the trans; the reaction was retarded by the presence of free PPh, or CO. The implications with respect to the mechanism of CS2 insertion are discussed. Scheme I

Introduction Preparative routes to thiolato complexes of the type C p W (CO),SR, where C p = $-cyclopentadienide and R = alkyl and aryl, a r e well developed.* A s part of our studies on polysulfano tungsten3 complexes, the triphenylphosphine-substitutedcomplexes CpW(CO),(PPh,)SR were required. Those with R = C6H, and 4-C6H,Me have recently been prepared via a complicated photochemical route and were not isolated in t h e pure state.4 This paper reports the preparation of the desired complexes by a mild and general route. The presence of the triphenylphosphine ligand renders the complexes susceptible to further reactions. Specifically, it was found that CS2easily inserts into the tungsten-thiolate bond to give t h e thioxanthate complexes C p W ( C 0 ) 2 S 2 C S R .

0

' ,

Treatment of CpW(C0)2(PPh,)H5 in THF a t 0 OC, first with (a) McGill University. (b) Concordia University. (2) Watkins, D. D.; George, T. A. J . Organomet. Chem. 1975, 102, 7 1 . (3) (a) Shaver, A.; Hartgerink, J. Can. J . Chem. 1987, 65, 1190. (b) Shaver, A,; Hartgerink, J.; Lai, R. D.; Bird, P.; Ansari, N. Organometallics 1983, 2, 938. (4) Weinmann, D. J.; Abrahamson, H. B. Inorg. Chem. 1987, 26, 2133.

+ R

S - : b

e o I

7

- PPh3

cs2 +

SR 2a-c __

0

c 7 ' T S . R C PPh3

0

la R b R

= CHMe2 = CH2Ph

R = 4-C H Me 6 4 R = C6H5

(1)

0020-1669/89/1328-1900!$01.50/0

1

L

I

0

Results

"3

MeLi and subsequently with RS(phth),6 where phth = phthalimido, gave the complexes CpW(CO),PPh,SR (la-d) (Scheme

0 1989 American Chemical Society